Compositions and methods for the protection of substrates from heat flux and fire

ABSTRACT

A flame or heat flux protective coating composition, which includes a dispersion of fiberglass, hollow glass spheres, or a combination of both in silicone. A flame or heat flux protective sheet, which includes hollow glass spheres dispersed in silicone in a sheet form or fiberglass and silicone in a sheet form, wherein the fiberglass is dispersed in the silicone or the fiberglass is a woven cloth coated with the silicone is also presented. Articles incorporating the flame or heat flux protective coating or sheet form and methods for coating an article with the flame or heat flux protective coating composition are also presented.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. § 119(e) to U.S.Provisional Application Ser. No. 61/120,142, filed Dec. 5, 2008; andthis application is a continuation-in-part of International ApplicationNo. PCT/US2007/074974, filed Aug. 1, 2007, which claims priority under35 U.S.C. §119(e) to U.S. Provisional Application Ser. No. 60/834,696,filed on Aug. 1, 2006, the disclosures of all of which are incorporatedherein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

The U.S. Government has a paid-up license in this invention and theright in limited circumstances to require the patent owner to licenseothers on reasonable terms as provided for by the terms of grantW15QKN-06-P-0262 awarded by the United States Army.

BACKGROUND OF THE INVENTION

Thermal barrier coatings (TBC) insulate and protect a substrate fromprolonged or excessive heat flux and enable the substrate material toretain its mechanical property integrity during service. Selection ofthe type of system and its components depends upon the application. Heatmay be dissipated away from a substrate by several methods, includingheat sinks, active cooling, transpiration cooling, radiation cooling,and intumescence.

A need exists for a coating that is able to protect a substrate fromexposure to high temperatures and possesses a high strain to failure(i.e. toughness) and adhesion capabilities under harsh, coldtemperatures while subject to high mechanical stresses.

SUMMARY OF THE INVENTION

The present invention is directed to a flame or heat flux protectivecoating composition, which includes a dispersion of fiberglass, hollowglass spheres, or a combination of both, in silicone. Also presented isa flame or heat flux protective sheet, which includes fiberglass, hollowglass spheres, or a combination of both and silicone in a sheet form,wherein the fiberglass and/or hollow glass spheres are dispersed in thesilicone or the fiberglass is a woven cloth coated with the silicone. Amethod for coating an article with a flame or heat flux protectivecoating and articles incorporating the flame or heat flux protectivecoating or sheet form are also presented.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of viscosity versus shear rate for various siliconeproducts;

FIG. 2 is a graph of viscosity versus shear rate for three glasscomponent/silicone coatings;

FIG. 3 is a graph of viscosity versus shear rate for various hollowglass sphere/silicone coatings.

FIG. 4 is a table setting forth descriptions of the tested coatings;

FIG. 5 is a graph of temperature versus time for the flame test forfiberglass/silicone coatings;

FIG. 6 is a graph depicting average flame test results forfiberglass/silicone coatings;

FIG. 7 is a graph depicting flame test results for hollow glasssphere/silicone coatings;

FIG. 8 is a graph depicting flame test results for hollow glasssphere/silicone coatings; and

FIG. 9 is a graph depicting a comparison of flame test results betweenan uncoated steel plate and plates coated with hollow glasssphere/silicone coatings.

DETAILED DESCRIPTION OF THE INVENTION

The present invention includes a “glass component,” which is defined toinclude fiberglass and/or hollow glass spheres. The glass componentimparts high emissivity to the composition of the present invention.Emissivity is a material's ability to absorb and radiate energy as afunction of its temperature and is defined herein as the ratio of thetotal energy radiated by a material to a black body at the sametemperature. A black body absorbs all electromagnetic radiation and isan ideal radiator with an emissivity of 1. The emissivities of allnon-black body objects are less than one and are determined by theobject's temperature, surface characteristics, geometric shape and size,and chemical composition. In order to dissipate heat, high emissivityvalues close to one are desirable. The emissivity of glass ranges from0.87-0.95.

The glass component also provides the coating composition withrelatively low heat conductivity and, thus, a high thermal insulationvalue. For example, one end of a strand of fiberglass is able to radiateheat away from a coated substrate when subjected to high temperatures,while the other end of the same strand insulates the substrate from theradiated heat. In another example, exposure of hollow glass spheres tohigh temperatures causes the spheres to melt together to form aprotective layer above the coated substrate.

The glass component is present in an amount suitable to promoteeffective radiation cooling when exposed to heat. In one embodiment,fiberglass is present in an amount from about 4% to about 14% by weightof the composition. Preferably, the amount of fiberglass is from about8% to about 14% by weight of the composition, more preferably from about8% to about 12% by weight of the composition.

In another embodiment, hollow glass spheres are present in an amountfrom about 0.1% to about 40% by weight of the composition. The amount ofhollow glass spheres affects the coating's viscosity and may depend uponthe desired method of application. For example, a preferred amount ofhollow glass spheres in a coating to be applied by spraying is fromabout 0.25% to about 20% by weight of the composition. A preferredamount of hollow glass spheres in a coating to be applied by a dippingmethod is from about 5% to about 30% by weight of the composition. Theamount of hollow glass spheres in a coating to be applied with a foambrush is up to about 40% by weight of the composition.

The fiberglass can have any suitable fiber length and diameter. Thefiberglass can also include fibers having a mixture of suitable lengthsand diameters. Preferably, the fiber length ranges from about 1 mm toabout 20 mm. A preferred fiber diameter ranges from about 6 μm to about19 μm. Optionally, at least a portion of sizing material is removed fromthe fiberglass prior to combining with the silicone component.

The hollow glass spheres can have any suitable diameter or mixture ofsuitable diameters. A preferred diameter for the hollow glass spheresranges from about 5 μm to about 30 μm, with about 18 μm being the mostpreferred diameter.

The glass component can have any suitable aspect ratio. In oneembodiment, the aspect ratio of the glass component is from about 1:1 toabout 20:1.

The silicone component provides the coating with mechanical flexibilityand thermal stability over a broad temperature range (e.g. −110-400°F.). Additionally, the decomposition of the silicone component at hightemperatures (e.g. greater than 400° F.) into silicon dioxide andsilicon oxide absorbs a large amount of energy from the heat source.Furthermore, as a result of silicone degradation, large surface areas ofthe glass component are exposed. The matted network of exposedfiberglass or exposed hollow glass spheres increases the coating'sdegree of radiative cooling and serves as insulation by remaininggrounded in the cooler under layers of silicone near the protectedsubstrate surface.

Preferably, the silicone component includes dimethylsiloxane andpolydimethylsiloxane.

For application to thermoplastic substrates, low viscosity siliconeswith solvents are preferred because they obviate the need to addmaterial that enhances the bond between the silicone and the substrate,require less energy to mix than higher viscosity silicones, and areeasier to apply to the substrate. For example, Dow Corning® 236Dispersion was observed to adhere well to polyethylene and polystyrene.When using thicker silicones (e.g. viscosity greater than 100 Pa·s andshear rate between about 1 and about 1000 s⁻¹) with a lower volatileorganic compound content (e.g. less than 1% VOC content) the addition ofpolyurethane enhances bonding to the surface of a thermoplasticsubstrate. For example, mixtures of silicone rubber and up to 70%polyurethane performed well during a flame test. If high toughness atlow temperatures is required, the maximum allowable concentration ofpolyurethane is 40% in order to pass a low temperature flexural test inwhich the coated substrate is bent around a 0.64 cm mandrel to 180° at−79° C.

The glass component and silicone are mixed or blended utilizingtechniques suitable for the viscosity of the silicone in the coatingcomposition. Blends that include a higher viscosity silicone can beprepared with more powerful blending means (e.g. a paddle mixer, singleor twin screw mixer, a Banbury mixer, and the like). Blends that includea lower viscosity silicone can also be prepared with the previouslydescribed blending means or by hand mixing in a container with astirring means or shaking the mixture in a closed container.

Another aspect of the current invention includes a method for applying aflame or heat flux protective coating composition to at least a portionof an article, wherein the composition includes a fiberglass dispersionin silicone. In a preferred embodiment, the coating is applied bybrushing onto a substrate. Medium viscosity silicones (e.g. Dow Corning®734 Flowable Sealant) are preferred when the coating is applied bybrush. In another embodiment, the coating is applied by dipping asubstrate into the coating composition. In yet another embodiment, thecoating is applied by spraying the coating composition onto a substrate.For spray coating applications, lower viscosity silicone rubbers (e.g.Dow Corning® 236 Dispersion) are preferred. When applying the coating,an even layer is not critical but the coating should be thick enough toobstruct vision of the underlying surface. For thicker coatings (e.g.for fire blocks), a high viscosity silicone (e.g. Silicone 1® (GE)) ispreferred.

Another aspect of the current invention includes an article, wherein atleast a portion is coated with a composition, which includes afiberglass dispersion, a dispersion of hollow glass spheres, or acombination of both in silicone.

Suitable substrates for the coated article include, for example,thermoplastics, thermoplastic composites, polyethylene, wood, stone,metal (e.g. steel), ceramics, glass, masonry materials (e.g. brick,marble, granite, travertine, limestone, concrete block, glass block,tile, etc.), and the like. For example, U.S. Pat. Nos. 6,191,228,5,951,940, 5,916,932, 5,789,477, and 5,298,214 disclose structuralrecycled plastic lumber composites made from post-consumer andpost-industrial plastics, in which polyolefins are blended withpolystyrene or a thermoplastic coated fiber material such as fiberglass.The disclosures of all five patents are incorporated herein byreference.

The coated article can have any shape or form, for example, a roundcross-section, a rectangular cross-section, an hourglass cross-section,a sheet form, or a combination thereof. Exemplary forms for plasticcomposites are disclosed in U.S. Application No. 60/486,205 filed Jul.8, 2003, U.S. Application No. 60/683,115 filed May 19, 2005, U.S.application Ser. No. 10/563,883 filed Jan. 9, 2006, and InternationalApplication No. PCT/US06/19311 filed May 19, 2006. The disclosures ofall of which are incorporated herein by reference. In one embodiment,the article is an L-Beam, I-Beam, a C-Beam, a T-Beam, or a combinationthereof.

Exemplary articles suitable for coating with the composition of thepresent invention include, but are not limited to, steel ammunitionboxes, railroad ties, plastic piping, lumber, sheet piling, boat hulls,pick-up truck beds, gasoline canisters, fuel tanks in automobiles,airplanes, ships, and submarines, steel skyscraper structures, bridges,areas near high temperature operating components, such as ignitionchampers, infrastructure, for example, building support structures andcables in suspension bridges, high-pressure storage tanks, and the like.

The composition of the present invention can also be incorporated into asheet form. For example, the silicone and glass components can becombined in an extruder and extruded into a sheet die. In anotherembodiment, a woven fiberglass cloth is coated with the siliconecomponent.

Exemplary applications for the sheet forms of the present inventioninclude, but are not limited to, fabrics, for example, fire protectiveclothing and blankets, and sheets applied to any of the articlesmentioned above as being suitable for coating with the composition ofthe present invention.

The following non-limiting examples set forth herein below illustratecertain aspects of the invention.

EXAMPLES Example 1 Viscosity Versus Shear Rate of Silicone

The viscosity versus shear rate of three types of silicone (Silicone 1®(GE), Dow Corning® 236 Dispersion, and Dow Corning® 734 FlowableSealant) is presented in FIG. 1. Viscosity and shear rate weredetermined using a TA Instruments AR-2000 rheometer. The compositionswere subject to a frequency sweep test from 100 to 0.01 Hz at a constanttemperature of 23° C. and constant % strain. The % strain value wasselected within the linear viscoelastic region, determined for eachmixture by a stress sweep test over a range of 1 to 10,000 μNm at aconstant frequency of 1 Hz and constant temperature of 23° C.

The highest viscosity silicone is Silicone 1® (GE) followed by DowCorning® 734 Flowable Sealant and Dow Corning® 236 Dispersion. DowCorning® 236 Dispersion possesses a significantly lower viscosity thanthe other two types of silicone.

Example 2 Viscosity Versus Shear Rate of Silicone Containing Fiberglassor Hollow Glass Spheres

Rheology experiments were performed to determine viscosity of thecoating at various concentrations of glass and with various types ofsilicone. Compositions were prepared by blending the glass component andsilicone. Viscosity and shear rate experiments were conducted as setforth in Example 1.

The viscosity versus shear rate of three types of fire retardantcoatings is shown in FIG. 2 for comparison, including 10/90%Fiberglass/Silicone 1®, 10/90% 3M™ iM30K Hi-Strength Glass Bubbles/DowCorning® 734 Flowable Sealant, and 10/90% 3M™ iM30K Hi-Strength GlassBubbles/Dow Corning® 236 Dispersion. This viscosity of the 10/90% 3M™iM30K Hi-Strength Glass Bubbles/Dow Corning® 236 Dispersion fireretardant coating is significantly lower than that of 10/90%Fiberglass/Silicone 1® and 10/90% 3M™ iM30K Hi-Strength GlassBubbles/Dow Corning® 734 Flowable Sealant.

Coating compositions containing 3M™ iM30K Hi-Strength Glass Bubbles(e.g. hollow glass microspheres) at 0, 10, 20, 30, and 40% by weight ofthe total composition in Dow Corning® 236 Dispersion were prepared byblending the microspheres and silicone.

The viscosity versus shear rate of the coating containing 3M™ iM30KHi-Strength Glass Bubbles in Dow Corning® 236 Dispersion is shown atvarious percentages of glass microspheres, including 0, 10, 20, 30, and40% glass in FIG. 3. The coating's viscosity increases with the additionof glass microspheres.

Example 3 Sample Preparation (Fiberglass in Silicone)

Blends of 4, 6, 8, 10, 12, and 14% by weight fiberglass in silicone,with trace amounts of silicone oil, were prepared. The components wereblended in a mixer and applied to a steel coupon with a putty knifetargeting a thickness of 1.6 mm or less. The fiberglass/siliconecoatings were compared against seven commercial products (FIG. 4) in alow temperature flexural test and a direct high temperature flame test.The coatings were applied to standard 76 by 152 by 0.735 mm steelcoupons. Three specimens per sample, or coating type, were tested forboth experiments.

Example 4 Sample Preparation (Hollow Glass Spheres in Silicone)

Blends of 0.1, 1, 3, 5, 10, 15, 20, 30, and 40% by weight 3M™ iM30KHi-Strength Glass Bubbles in Dow Corning® 236 Dispersion were prepared.The components were blended in a mixer and applied to standard 76 by 152by 0.735 mm steel coupons using one of three methods targeting athickness of 1.6 mm or less: painted with a foam brush, applied with aplastic putty knife, or dipped.

Example 5 Low Temperature Flexural Test

Coated steel plates were annealed in dry ice, approximately −79° C., forat least 15 minutes followed by bending around a 0.64 cm mandrel to anangle of 180°. During the test, photographs were taken of each specimenat 30°, 90°, and 180° of bending. Visual observation providedinformation about a coating's response to thermal shock when bonded to asteel substrate and indicated the type and severity of surface damageincurred due to bending at low temperatures. A successful coating didnot have surface damage after testing.

During bending, the coating stretches to accommodate the substrate'snew, larger surface area. The surface of the coating is in tension andreceives the highest percent strain during bending. Thus, crackformation is initiated at the coating surface. Failure of the coating isindicated by crack development and propagation in the coating anddelamination. Common modes of failure included tiny crack formationparallel to the bending axis in the deformation region, large cracksthat caused pieces of the coating to detach and expose the substrate,and some brittle failure. In some cases, the coating delaminated aswell. These types of surface failure indicate a coating with low strainto failure at low temperatures that will detach or delaminate, exposethe substrate, and create a point source of radiative heat.

As indicated in FIG. 4, Products A, B, C, D, E, and G failed the lowtemperature flexural test due to crack formation. At more severe bendingangles, the initial cracks simply propagated, caused pieces of thecoating to detach from the substrate, and/or the coating delaminated. Inthe Product C sample, 2 of 3 specimens passed, and in the Product Gsample, 1 of 3 specimens passed. However, all specimens per sample mustpass the test in order to be considered successful. Product H, asilicone-based coating, is the only commercial coating tested that didnot suffer any surface damage and passed the low temperature flexuraltest. The fiberglass/silicone composite coating did not suffer anysurface damage, remained adhered to the substrate during bending, andpassed the low temperature bend test. The coating thickness does notappear to significantly affect low temperature performance. For ProductE and the fiberglass/silicone composite, specimens were prepared atvarious thicknesses. All Product E specimens failed while allfiberglass/silicone composite specimens passed.

All compositions of 3M™ iM30K Hi-Strength Glass Bubbles in Dow Corning®236 Dispersion successfully passed the low temperature flexural test(FIG. 4).

Example 6 Flame Test

A flame produced by a propane torch was applied normal to the coatedside of a specimen. An IR sensor (Omega OS550 Series Infrared IndustrialPyrometer) was aligned on the same axis as the flame and measuredtemperature as a function of time on the back side of the vertical steelcoupon. The inner cone length of the flame was adjusted to 3.175 cm, andthe tip of the inner cone, the hottest part of the flame, was positioneddirectly on the sample's surface 2.54 cm above the bottom edge and atthe center across the sample width. This configuration delivered worstcase scenario results for high temperature direct point heating. Theadiabatic flame temperature of propane in air is approximately 1,927°C.+/−38° C. The flame was applied for a total duration of ten minutes. Acoating is considered to fail the flame test if the maximum temperaturedetected by the IR sensor exceeds 316° C. The maximum temperaturereached for each coating was compared against the control specimen, anuncoated steel plate, as a point of reference.

The flame test results are presented graphically in FIGS. 4-9. Theaverage temperature versus time data collected during the flame test foreach sample (i.e. fiberglass/silicone coating and commercial product) ispresented in FIG. 5, and the average maximum temperature and standarddeviation per sample in FIG. 6. The 12% fiberglass/silicone coatingmaintained the lowest maximum temperature of all of the coatings. InFIG. 6, the black horizontal line signifies the pass/fail temperaturelimit of 316° C. and delineates the coatings that passed the flame testfrom those that did not (e.g. coatings with a maximum temperature belowthe line pass, while those above the line fail).

Coatings with a maximum temperature below the limit were Products D andE and the fiberglass/silicone composite coatings (excluding the 6%fiberglass composition) (FIG. 4). The average maximum temperatures ofProducts A, B, C, F, G, and H exceeded the limit, thus failing the test.

The maximum temperature for the coatings containing 3M™ iM30KHi-Strength Glass Bubbles in Dow Corning® 236 Dispersion obtained duringthe 10-minute flame test is shown in FIG. 7. Coating thickness rangesfrom 0.25-0.8 mm for these flame test specimens. The maximum temperatureachieved drops by 100° C. with the addition of the hollow glassmicrospheres. Thicker coatings provide increased protection and wouldresult in a lower maximum temperature.

The maximum temperature for the coatings containing 10, 15, and 20% byweight 3M™ iM30K Hi-Strength Glass Bubbles in a matrix of Silicone 1®obtained during the 10-minute flame test is shown in FIG. 8. Coatingthickness ranges from 1.14-1.19 mm for these flame test specimens.

FIG. 9 presents a comparison of the 10-minute flame test between DowCorning® 236 Dispersion and Silicone 1® containing 10% 3M™ iM30KHi-Strength Glass Bubbles in each silicone matrix. Flame test results ofan uncoated steel coupon are also provided. Flame testing indicates thatvarious fully-cured silicone rubbers essentially performed the same.Thus, any silicone rubber may be used depending on the desiredapplication method.

The foregoing examples and description of the preferred embodimentsshould be taken as illustrating, rather than as limiting the presentinvention as defined by the claims. As will be readily appreciated,numerous variations and combinations of the features set forth above canbe utilized without departing from the present invention as set forth inthe claims. Such variations are not regarded as a departure from thespirit and script of the invention, and all such variations are intendedto be included within the scope of the following claims.

1. A flame or heat flux protective coating composition comprising adispersion of fiberglass, hollow glass spheres, or a combination of bothin silicone.
 2. The composition of claim 1, wherein said compositioncomprises fiberglass in an amount from about 8% to about 14% by weightof the composition.
 3. The composition of claim 2, wherein saidfiberglass is present in an amount from about 8% to about 12% by weightof the composition.
 4. The composition of claim 1, wherein saidcomposition comprises hollow glass spheres in an amount from about 0.1%to about 40% by weight of the composition.
 5. The composition of claim4, wherein said hollow glass spheres are present in an amount from about0.25% to about 20% by weight of the composition.
 6. The composition ofclaim 4, wherein said hollow glass spheres are present in an amount fromabout 5% to about 30% be weight of the composition.
 7. The compositionof claim 1, wherein said composition comprises fiberglass fibers havinga length from about 1 mm to about 20 mm.
 8. The composition of claim 1,wherein said composition comprises fiberglass fibers having a diameterfrom about 6 μm to about 19 μm.
 9. The composition of claim 1, whereinsaid composition comprises hollow glass spheres of a diameter from about5 μm to about 30 μm.
 10. The composition of claim 1, wherein saidcomposition comprises fiberglass wherein at least a portion of sizingmaterial has been removed from said fiberglass.
 11. An articlecomprising at least a portion of a surface coated with the compositionof claim
 1. 12. The article of claim 11, wherein the surface comprises amaterial selected from the group consisting of metal, thermoplastics,thermoplastic composites, polyethylene, wood, stone, ceramics, glass,masonry materials, and combinations thereof.
 13. The article of claim11, wherein said article is selected from the group consisting of steelammunition boxes, railroad ties, plastic piping, lumber, sheet piling,boat hulls, pick-up truck beds, gasoline canisters, fuel tanks inautomobiles, airplanes, ships, and submarines, steel skyscraperstructures, bridges, areas near high temperature operating components,infrastructure, building support structures, cables in suspensionbridges, and high-pressure storage tanks.
 14. A flame or heat fluxprotective sheet comprising hollow glass spheres dispersed in siliconein a sheet form or fiberglass and silicone in a sheet form, wherein thefiberglass is dispersed in the silicone or the fiberglass is a wovencloth coated with the silicone.
 15. An article comprising the sheet ofclaim 14, wherein the article is selected from the group consisting offabrics, steel ammunition boxes, railroad ties, plastic piping, lumber,sheet piling, boat hulls, pick-up truck beds, gasoline canisters, fueltanks in automobiles, airplanes, ships, and submarines, steel skyscraperstructures, bridges, areas near high temperature operating components,infrastructure, building support structures, cables in suspensionbridges, and high-pressure storage tanks.
 16. The article of claim 15,wherein said fabric is incorporated in fire protective clothing or afire protective blanket.
 17. A method for coating an article with aflame or heat flux protective coating layer comprising applying thecomposition of claim 1 to at least a portion of said article.